Table Of ContentHandbook of Crystal Growth
Thin Films and Epitaxy: Basic Techniques
VOLUME III, Part A
Second Edition
Editor-in-Chief
Tatau Nishinga
The University of Tokyo
Hongo, Bunkyo-ku, Tokyo, Japan
Volume Editor
Thomas F. Kuech
University of Wisconsin- Madison
Department of Chemical and Biological Engineering
Madison, WI
USA
Amsterdam(cid:129)Boston(cid:129)Heidelberg(cid:129)London
NewYork(cid:129)Oxford(cid:129)Paris(cid:129)SanDiego
SanFrancisco(cid:129)Singapore(cid:129)Sydney(cid:129)Tokyo
Handbook of Crystal Growth
Thin Films and Epitaxy: Materials, Processes,
and Technology
VOLUME III, Part B
Second Edition
Editor-in-Chief
Tatau Nishinga
The University of Tokyo
Hongo, Bunkyo-ku, Tokyo, Japan
Volume Editor
Thomas F. Kuech
University of Wisconsin- Madison
Department of Chemical and Biological Engineering
Madison, WI
USA
Amsterdam(cid:129)Boston(cid:129)Heidelberg(cid:129)London
NewYork(cid:129)Oxford(cid:129)Paris(cid:129)SanDiego
SanFrancisco(cid:129)Singapore(cid:129)Sydney(cid:129)Tokyo
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Firstedition1993
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Thecrystalsonthefrontcoverarehigh-qualitysyntheticdiamondcrystalsgrownbySumitomoElectricIndustries,LTDbya
temperaturegradientmethodunderhighpressureandhightemperature.Theyellowishcrystalsareordinarilysynthetic
diamondscontainingnitrogenimpurityofseveraltensofppm(typeIb).Thecolorlessonesarehigh-puritysyntheticdiamonds
freeofimpurities(typeIIa).Thesizeofthelargesthigh-puritycrystal(lowerleft)isabout12mmindiagonallength.Thephoto
wasprovidedbyDr.HitoshiSumiya.
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General Preface
The history of crystal growth is long as those of the universe and the earth. Meteorites
contain pyrites and olivine crystals which indicate these crystals were grown when the
planets were born. Crystals naturally produced are used as gems from the early time of
the human history. In Exodus, it is written that breast-piece was decorated by ruby,
emerald, sapphire,amethyst, and othergems.
Therearealotofcrystalsaroundus.Asexamples,wecanfindsnowflakesfallingdown
from the sky, ice crystals in a lake in winter, salt and sugar crystals in the pots of our
kitchen. But, it was after the invention of point contact and junction transistors,
respectivelyin1947and1948,thattheindustrypaidagreatinterestonthecrystalgrowth.
Withoutthegrowthofhighpurityandhighlyperfectsingle-crystalsemiconductor,atthat
time of Ge, theinvention ofthetransistors will never happen.
It is well known that the modern information society will be not realized without
electronic and optical devices. One finds large-scale integrated circuits of Si in every
computer from laptop to super computers. For high speed and mass transmission of
information, compound semiconductor devices are indispensable.
Thesedevicesarefabricatedalmostallbyusingsinglecrystalsofsemiconductorsand
oxides.Whenwelook intothehistory ofthedevices, wealwaysseethataninventionof
crystal growth technique makes it possible to bring out new device. As we saw, the
inventionoftransistorwaspossibleonlyafterthegrowthofhigh-qualityGesinglecrystal.
The growth of large-diameter dislocation-free Si crystal has enabled the production of
large-scale integrated circuit. Due to the invention of liquid-phase epitaxy, it became
possible to realize light-emitting diode (LED) and laser diode (LD) in real use. Drastic
technologicalimprovementinhighlylatticemismatchheteroepitaxymadeitpossibleto
realizebluewultravioletLEDandLDanditcanbesaidthatthesuccessinthegrowthof
high-quality nitride semiconductor gave the blue light all over the world. Hence, we
should understand that new technology of crystal growth has always created new elec-
tronic and optical devices.
Itisextremelygoodnewsforthecommunityofcrystalgrowththat2014NobelPrizein
Physics was awarded to Professors Isamu Akasaki, Hiroshi Amano and Shuji Nakamura
for the invention of efficient blue light-emitting diodes which has enabled bright and
energy-saving white light sources. This invention is based on the growth of nitride
semiconductors employing a low-temperature buffer layer on sapphire substrate in
heteroepitaxy. We are happy that Professor Hiroshi Amano, one of the winners, is con-
tributing to this Handbook as anauthor ofChapter 16 inVol. IIIA.
ix
x GENERAL PREFACE
The first edition of the Handbook of Crystal Growth was edited by D.T.J. Hurle. This
Handbook was composed of three volumes and published in 1993–1994. The present
secondeditionoftheHandbookalsoconsistsofthreevolumes.Eachvolumewasedited
byseparate editors.VolumeIis edited by T.Nishinaga andthe volume coversthebasic
aspectsofcrystal growth.InVolumeIa,fundamentalsandkineticsofcrystalgrowthare
describedandin1b,advancedproblemsoftransportandstabilityarediscussed.Volume
IIiseditedbyP.Rudolphandthisvolumecoversbulkcrystalgrowth.VolumeIIapresents
basic technologies of bulk growth and IIb does growth mechanism and dynamics.
VolumeIIIwaseditedbyT.F.Kuechandthevolumecoversthinfilmgrowthandepitaxy.
Volume3adiscussesbasictechniquesandIIIbdoesgrowthmechanismsanddynamics.
Present Handbook project was created in March, 2011 and six advisors were
appointed.TheyareT.F.Kuech,G.B.Stringfellow,J.B.Mullin,J.J.Derby,R.Fornari,and
K. H.Ploog.Iam very muchgratefulfor their important and valuable suggestions.
Finally, all editors would like to express their sincere thanks to Shannon Stanton,
Elsevier,for herstrongand well cared supportto this work.
Tatau Nishinaga
(Editor inChief)
Preface to Volume III
VolumeIIIoftheHandbookhasboththeenablingscienceandkeyapplicationsofepitaxy
and thin film formation. Epitaxy is the formation of a crystal, typical in thin film form,
through deposition on a substrate wherein the film and the substrate have well-defined
structural registry. Epitaxy is key to many of our advanced technologies associated with
electronics, optics, optoelectronics, energy, and a range of specialty applications. As a
crystal growth process, epitaxy draws upon the basic science underpinning all forms of
crystalgrowthasdiscussedinVolumesIandII.VolumeIIIconsistsoftwoseparateparts.
Volume IIIA generally describes the underlying principles behind many of the epitaxial
growthtechniquesincurrentuse.Theprocessofepitaxialgrowthcantakeplacefroma
solid,liquid,orvaporphaseenvironment.Thevaporphaseenvironmentcanspanfrom
ultra-high vacuum to well above atmospheric pressure. While each of these crystal
growthenvironmentsissomewhatunique,partofourcurrentunderstandingiscommon
to all of these. Volume IIIB focuses on specific materials systems or techniques classes
thatprovidematerialsthatareofdirectcurrenttechnologicalimportanceorproducevery
particular nano- or microstructures. The development of these materials is usually
throughapreferredepitaxialgrowthtechnique;however,multipletechniqueshavebeen
used for almost all materials, depending on materials composition, structure, and
propertiesrequired.
In Volume IIIA, Chapter 1 discusses the use of epitaxial techniques and materials
impacting the growingareaof energy-relatedapplications. Inmany ways, energy appli-
cations encompass many of the structures and materials used in other technologies.
Commercially,vaporphaseprocessinghasbeenextensivelyexploitedduetoitsabilityto
formepitaxialmaterialsoverlargeareaswithaneasilycontrolledeffluentwastestream.
Chapters 2–6 describe the two most commonly used paper phase techniques and the
underlying transport and chemical kinetic issues associated with them. Metal organic
vapor phaseepitaxy is particularly importantfor its use inthe formation ofcommercial
optoelectronic devices such as light-emitting diodes and epitaxial solar cells. Molecular
beam epitaxy, using a variety of sources, is described in Chapters 7 and 9, with the
underlying principles and phenomenology presented in Chapter 8. Other growth envi-
ronmentsarealsousedtoproduceepitaxymaterialssuchasgrowthfromtheliquidphase
thatisdescribedinChapter10andfromthesolidphasedescribedinChapter11.While
epitaxial growth has been typically associated with the formation of a film on a planar
substrate, the development of three-dimensional structures, such as quantum dots,
wires, rods, as well as other interesting and useful morphological structures, is increas-
ingly important. The approaches to achieving these structures are discussed in
xi
xii PREFACE TO VOLUME III
Chapters12–16.Chapter16isofparticularnoteasitfeaturesworkbyoneofthewinners
of the 2014 Nobel Prize in Physics that was highlighted by the Nobel committee. These
various approaches have been used to incorporate such three-dimensional features
within adevice structure to achieve new types and levels of performance.
Volume IIIB focuses on specific techniques used in epitaxial growth to extend the
rangeofgrowthconditions,reducedefects,andcharacterizetheelectronicandstructural
propertiesoftheepitaxialstructure.Inaddition,importantspecificmaterialssystemsare
discussed as both examples of epitaxial growth and to highlight these technologically
important processes. Chapter 17 discusses the use of transitional epitaxial structures to
provide surfaces possessing a lattice parameter not easily achievable by bulk crystal
growthtechniques.Anaspectoftheseepitaxialgrowthprocessesallowingavarietyoflow
stabilityormetastablematerialstobegrownreliesonthemodulationorrapidswitching
ofgrowthsources,allowingatomiclayercontroloverthefilmdevelopment,aspresented
in Chapter 18. Chapters 19–21 present aspects of materials properties and character-
ization. During and after these films are synthesized, rigorous and precise character-
ization,typicallyutilizingX-raydiffraction,opticaltechniques,andothertoolstoevaluate
structuralandelectronicproperties,areemployed.Theremainingchaptersfocusonthe
detailedconsiderationofacross-sectionofmaterials.Epitaxyhasnowbeenappliedtoa
wide variety of materials from organic molecules (Chapter 27), refractory semi-
conductors,suchasnitrides,SiC,anddiamond(Chapters25,26,31,32),oxides(Chapter
28), two-dimensional materials (Chapters 29 and 30), and more conventional materials
(Chapters22–24).
Together, these chapters present a broad and deep picture of the processes and
applications of this important form of crystal growth. As a technology, its application
fieldswillcontinuetogrow andextendtoamorediversesetofmaterials andcontrolof
the physical structure and morphology, allowing near-atomic control over the material
structure.
ThomasF. Kuech
Editor HB ofCrystal Growth,
VolumeIIIA and IIIB
List of Contributors
Hiroshi Amano
Department of Electrical Engineering and Computer Science,
Akasaki Research Center, Nagoya University, Nagoya, Japan
Yamina André
ClermontUniversité,UniversitéBlaisePascal,InstitutPascal, Clermont-
Ferrand, France; CNRS, UMR 6602, Aubière, France
Hajime Asahi The Institute of Scientific and Industrial Research, Osaka University,
MIHOGAKA, IBARAKI, Osaka, Japan
John E. Ayers
Electrical and Computer Engineering Department, University of
Connecticut, Storrs, CT, USA
Michael J. Aziz
Harvard School of Engineering and Applied Sciences, Cambridge, MA,
USA
Bhavtosh Bansal
Dept. of Physical Sciences, Indian Institute of Science Education and
Research Kolkata, India
Arnab Bhattacharya
Dept. of Condensed Matter Physics and Materials Science, Tata
Institute of Fundamental Research, Mumbai, India
Robert M. Biefeld
Sandia National Laboratories, Albuquerque, NM, USA
A.A. Bol
Department of Applied Physics, Eindhoven University of Technology,
Eindhoven, The Netherlands
April S. Brown
Department of Electrical and Computer Engineering, Pratt School of
Engineering, Duke University, Durham, NC, USA
Robert Cadoret
Clermont Université, Université Blaise Pascal, Institut Pascal,
Clermont-Ferrand, France; CNRS, UMR 6602, Aubière, France
Jeffrey G. Cederberg
Sandia National Laboratories, Albuquerque, NM, USA
Xiaogang Chen
Department of Electrical and Computer Engineering, University of
Illinois, Urbana, IL, USA
Enrique D. Cobas
Materials Science and Technology Division, U.S. Naval Research
Laboratory, SW Washington, DC, USA
xiii
xiv LIST OF CONTRIBUTORS
James J. Coleman
Department of Electrical and Computer Engineering, University of
Illinois, Urbana, IL, USA
Armin Dadgar
Institute of Experimental Physics, Otto-von-Guericke-Universität
Magdeburg, Magdeburg, Germany
Paul G. Evans Materials Science and Engineering, University of Wisconsin–Madison,
Madison, WI, USA
Roberto Fornari
Department of Physics and Earth Sciences, University of Parma,
Parma, Italy
Hiroshi Fujioka
Institute of Industrial Science, The University of Tokyo
D. Kurt Gaskill
U.S. Naval Research Laboratory, Washington, DC, USA
Evelyne Gil
Clermont Université, Université Blaise Pascal, Institut Pascal, Clermont-
Ferrand, France; CNRS, UMR 6602, Aubière, France
Mark S. Goorsky
UCLA,HSSEASSchoolofEngineering&AppliedSciences,Department
of Materials Science and Engineering, Los Angeles, CA, USA
Brett C. Johnson
School of Physics, University of Melbourne, Victoria, Australia
W.M.M. Kessels
Department of Applied Physics, Eindhoven University of Technology,
Eindhoven, The Netherlands
Jeong Dong Kim
Department of Electrical and Computer Engineering, University of
Illinois, Urbana, IL, USA
Tsunenobu Kimoto
Department of Electronic Science and Engineering, Kyoto
University, Kyoto, Japan
H.C.M. Knoops
Department of Applied Physics, Eindhoven University of Technology,
Eindhoven, The Netherlands
G. Koblmüller
MaterialsDepartment, Universityof California, SantaBarbara, CA, USA;
WalterSchottkyInstitutand PhysikDepartment, TechnischeUniversitätMünchen, Garching,
Germany
Daniel D. Koleske
Sandia National Laboratories, Albuquerque, NM, USA
Alois Krost
Institute of Experimental Physics, Otto-von-Guericke-Universität
Magdeburg, Magdeburg, Germany
LIST OF CONTRIBUTORS xv
Thomas F. Kuech
Department of Chemical and Biological Engineering, University of
Wisconsin–Madison, Madison, WI, USA
J.R. Lang
Materials Department, University of California, Santa Barbara, CA, USA;
Electrical Engineering Department, Yale University, New Haven, CT, USA
Hongdong Li
State Key Laboratory of Superhard Materials, Jilin University,
Changchun, Jilin, China
Xiuling Li
Department of Electrical and Computer Engineering, Micro and
Nanotechnology Laboratory, University of Illinois, Urbana, IL, USA
Maria Losurdo
NationalCouncilofResearch,InstituteofInorganicMethodologiesand
of Plasmas, CNR-IMIP, via Orabona 4, 70126 Bari, Italy
Fumihiro Matsukura
WPI-Advanced Institute for Materials Research, Tohoku
University, Sendai, Japan; Center for Spintronics Integrated Systems, Tohoku University,
Sendai, Japan; Laboratory for Nanoelectronics and Spintronics, Research Institute of
Electrical Communication, Tohoku University, Sendai, Japan
Michael G. Mauk
College of Engineering, Drexel University, Philadelphia, PA, USA
Jeffrey C. McCallum
School of Physics, University of Melbourne, Victoria, Australia
Kathleen M. McCreary
NRC Postdoctoral Fellow Residing at U.S. Naval Research
Laboratory, SW Washington, DC, USA
Xin Miao
Department of Electrical and Computer Engineering, Micro and
Nanotechnology Laboratory, University of Illinois, Urbana, IL, USA
Osamu Nakatsuka
Department of Crystalline Materials Science, Graduate School of
Engineering, Nagoya University, Nagoya, Japan
Nathan Newman
Materials Program, Arizona State University, Tempe, AZ, USA
Tatau Nishinaga
The University of Tokyo, Japan
Hideo Ohno
WPI-AdvancedInstituteforMaterialsResearch,TohokuUniversity,Sendai,
Japan; Center for Spintronics Integrated Systems, Tohoku University, Sendai, Japan;
Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical
Communication, Tohoku University, Sendai, Japan
S.E. Potts
Department of Applied Physics, Eindhoven University of Technology,
Eindhoven, The Netherlands
